Terpyridine-based metallo-cuboctahedron nanomaterials for efficient photocatalytic degradation of persistent organic pollutants

Metal–organic cage photocatalysts with nanoscale dimensions have received wide attention in the field of photocatalytic environmental pollutant treatment due to their large cavities,easy modification,high tunability,and enriched active sites.Herein,we prepared a series of dihydroanthracene-cored terpyridine-based metallo-cuboctahedron nanomaterials through a selfassembly method,which exhibited satisfactory degradation performance for persistent organic pollutants under visible light irradiation.In particular,under light conditions,S1-Zn,one of the prepared nanomaterials,produced photogenerated holes oxidizing water molecules to∙OH,which attacked ibuprofen(IBU)for up to 95% degradation.Simultaneously,the corresponding photogenerated electrons reduced the dissolved oxygen in water,producing 66.2μmol/L hydrogen peroxide.The obtained supramolecular photocatalytic materials have a stable structure with non-precious metals and do not require a sacrificial agent.The metal sites of metallo-cuboctahedrons adsorb pollutants and transfer captured holes to them,accelerating degradation and promoting simultaneous H_(2)O_(2) production.This work not only proposes a simple and efficient synthesis method for supramolecular photocatalysts but also opens up opportunities for efficient,low-cost,and multifunctional materials for environmental persistent organic pollutants treatment.

Sandwich-like Heterochromophore Metallo-Supramolecules Based on Dense Chromophore Arrangements with Energy and Chirality Transfer Properties

Multichromophoric architectures with wellorganized chromophoric arrangements are of vital importance to gain insights into interchromophoric interactions.Herein,we report a novel heteroleptic self-assembly strategy and construct three achiral and one chiral sandwich-like heterochromophore complexes(Zn_(4)L^(G)L^(A-C)_(2)and Zn_(4)L_(G)L^(D)_(2)).Possible dynamic products,including homoleptic oligomers and isomers,are eliminated,producing achiral complexes with exceptional purity.Isomers are observed in chiral complexes due to the flexible geometry of LD.Perfectly aligned chromophore arrangements with precise spacing and orientations are evidenced by single-crystal X-ray diffraction.The distinct segments in the ligands lead to different interchromophoric interactions.Impressively,energy transfer and tunable emission,including white-light emission,are achieved for Zn_(4)L^(G)L^(A)_(2)and Zn_(4)L^(G)L^(B)_(2).In addition,chirality transfer is observed for Zn_(4)L_(G)L^(D)_(2),due to conformational restriction from chiral LD,leading to chiral rotational conformations of tetraphenylethylene moiety in LG.

From Mechanically Interlocked Structures to Host-Guest Chemistry Based on Twisted Dimeric Architectures by Adjusting Space Constraints

Mechanically interlocked molecules(MIMs)and host–guest chemistry have received great attention in the past few decades.However,it remains challenging to design architectures with mechanically interlocked features and construct cavities for guest molecule recognition using similar building blocks.In this study,we designed and constructed a series of novel twisted supramolecular structures by assembling various multitopic terpyridine(tpy)ligands with the same diameter and Zn(II)ions.The obtained complexes exhibited evolutional architectures and showed distinctively different space-constraint effects.Specifically,the assembled dimer SA,SB,and SBH displayed mechanically interlocked phenomena,including[2]catenane and[3]catenane,with an increase in concentration.However,no interlocked structures were observed in complexes SC and SCH constructed by hexatopic tpy ligands due to the significant space constraints.The single-crystal data of complex SCH further proved significant space constraints and illustrated the formation of a relatively closed cavity,which showed excellent host–guest properties for different calixarenes,especially high affinity for calix[6]arene.